TWI393736B - 加標籤之無機填充物及/或色素 - Google Patents

加標籤之無機填充物及/或色素 Download PDF

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TWI393736B
TWI393736B TW095125049A TW95125049A TWI393736B TW I393736 B TWI393736 B TW I393736B TW 095125049 A TW095125049 A TW 095125049A TW 95125049 A TW95125049 A TW 95125049A TW I393736 B TWI393736 B TW I393736B
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pigment
inorganic filler
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inorganic
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TW200706581A (en
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Ralf Eickschen
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Sachtleben Chemie Gmbh
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Description

加標籤之無機填充物及/或色素
本發明關於一種加標籤的無機填充物及/或色素、其製造方法及其應用。
特別是本發明的標的為加標籤的無機色素與填充料，以及其製造方法與應用。
在食品、飼料、醫藥以及許多工業產品有一種需求，即對其來源(Herkunft)作清楚地指示。因此，舉例而言，對於損害賠償(Reklamation)的目的，須證明原料是那一個製造商提供的。而反過來，提供者也希望能夠在損害賠償(Schadenersatzanspruch)錯誤地指向他們時，能藉清楚的來源證明而自保。舉例而言，在醫學上，對於該使用領域使用特別之合成的硫酸鋇作X光對比劑。在開發中國家時時用硫酸鋇產品(仿冒品)(Plagiate)作上述使用目的，它們係低品質者。當這些產品累積變多時，不免危害病人健康。因此高品質產品的製造商係望能不含糊且用最小功夫證明本身產品的使用，俾能在意外時自保以防不許可的償還索賠(Rgressanspruch)。
在先前技術中，習用技術有將提供的材料用以下方式加標籤：將其材料加入較大比例的重而穩定的同位素。在所有化合物中，構成它們的化學元素都由各種不同的穩定同位素組同，這些穩定同位素存在自然中，也以「自然分配比例」存在所要加標籤的材料中，所謂的「平均自然頻 度」(見表1，Chiaz,2005,39,93頁)，因此須加入(特別是混入)很高濃度之加標籤的物質，俾造成明顯的偏差。
在表中顯示這些元素及其穩定同位素，它們適用於將色素或填充劑加標籤，其相對平均頻繁度F〔F=(同位素量)/(Σ同位素量)〕、國際同位素標準的名稱、以及對於二種最頻繁出現的穩定同位素的同位素比例R〔R= (同位素a)/(同位素b)〕。但實際上，對於化合物中的各元素和所予之頻繁度只有很小的局部的及時間性的偏差。因此所有樣品(檢體)(Probe，英：specimen)的準確的同位素濃度係在Promille中用相對於各國際標準的朝對偏差用δ值表示。這表示：首先要測定各種不同色素與填充劑的相關同位素的δ值〔例如：對於BasO4係用18O/16O同位素比例對相關的標準V-SMOW或對ZnS用34S/32S同位素比例對相關的標準CDT〕，這點再被確定當作在所用的條件(所用的原料、製造條件)下這種化合物的自然同位素比例。
當依先前技術上標籤時，有一問題要考慮到，即：在所要加標籤的材料中之標籤同位素的比例，舉例而言，會受到程序技術的步驟減少。因此要鑑定來源的檢體如有必要可以稀釋。這點特別是在飼料及食品的場合(例如果汁)尤然。例如，當加入帶同位素標籤的水時，該水可藉乾燥或類似作用從要加標籤的材料除去。且在稀釋或乾燥後，穩定同位素的濃度須遠在自然發生的濃度之上或之下，俾能證明來源，其結果為要使用加了對應地高濃度的加以標籤同位素的物質，然而這點使得加標籤的物質消耗量大，且因而成本高。此外，特別是在食品的場合，由於不當地高濃度的加標籤的物質，而發生不能接受的毒性副作用。如果稀釋度任意提高，則可能該標籤物不再能測量。
由測量技術的立體，這種問題係部分地利用德專利OE-A-10200802的技術內容解決。但該方法只關於用加了 重氫(氘)的水加標籤。因此這種方法有一缺點，即當此加入的水至少部分地長時留在終產品中時，它才能使用。因此這種方法不能用於將無機填充物及/或色素(特別是色素與填充料)加標籤。它們在其製造及加工時作數次乾燥或作一道熱處理，其中往往溫度超過100℃(例如在聚合物材料押出成形時)。
因此本發明的目的在克服先前技術的缺點。
特別是本發明的目的在提供一種無機填充物及/或色素，它長時地利用一種或數種重而穩定的同位素加標籤，且提供其製造方法。本發明另一目的在提供一種無機填充物及/或色素，其用於作標籤的同位素的含量不會受熱理影響。
出乎意料地，這種目的可依本發明利用申請專利範圍主項的特點達成，較佳的進一步特點見於申請專利範圍附屬項。
為了在製造終產物時，該標籤狀況不會改善或失去，故該標籤須長時或牢固地建入該填充物及/或色素的化合物中學鍵結中。舉例而言，如果一種無機添加料如TiO2(舉例而言，它可當作白色素使用)在使用前只用以O18作標籤的水潤化，則該標籤狀況在製造終產物時只會部分地或甚至不會被帶入終產物中。如果在製造填充物及/或色素或終產物的程序中使用該填充物及/或色素的情形下包含一道熱步驟或脫水步驟，則上述優點可在使用加標籤的水時 經常達成。
用重而穩定的同位素加標籤的方式須選設成使終產物中的含量須能清楚地證明(例如利用穩定同位素質譜儀)，即使終產物只有幾毫克可用亦然。
在此，依本發明，該問題利用一種無機填充物及/或色素解決，該填充物及/或色素比起天然存在者有較高的(△δ為正值)或較低的(△δ為負值)比例的重而穩定的同位素，例如2H、13C、15N、18O及/或34S，該無機填充物及/或色素宜為一種色素或填充料。這種無機填充物及/或色素的例子有TiO2、ZnS或BaSO4。
標籤物係牢固地建入填充物及/或色素中。此處，「牢固地建入」表示：對一特定的填充物及/或色素，各△δ有恆定的值。此外，可依標的調整一定含量的重同位素，亦即調整一定的△δ。
在此△δ表示含較多重同位素的化合物與含較少重同位素的「天然」化合物的δ值的差(例如：用34S加標籤的ZnS的δ 34S減去「天然」ZnS的δ 34S。)
依本發明，此△δ值在3~1000‰間，且宜在5~300‰間，尤宜在10~200‰間及/或在-3~-100‰間，且宜在-5~-20‰間。
利用較高或較低比例的重同位素(例如2H、13C、15N、18O及/或34S)該材料可清楚而長時地上標籤及證明。當材料用二種或更多種同位素加標籤時，該各種用於作標籤的同位素全部增加或者全部減少，或者也可將一種或數種 同位素增加，而其他同位素減少。
該加標籤作業可利用各種不同方法達成，例如：
--將該無機填充物及/或色素在製造時，藉著將一適合的重而穩定的同位素建入化合物中而直接作長時上標籤。
--無機填充物及/或色素，特別是色素與填充料，往往作一道無機及/或有機式後處理，特別是將它們的粒子鍍覆一鍍層。受到這道後處理，填充物及/或色素的性質改變，使它們可最佳地配合使用目的(Jochen Winkler，「二氧化鈦」，專題34，漢諾威；Vincentz,2003；Elizabeth Reck，顏料&漆，102,Jahrgang 3/96,40~48頁)。且這些無機及/或有機式復處理也可用於用重而穩定的同位素作長期的上標籤。
--填充料與色素，例如TiO2、ZnS或BaSO4(用無機方式作過後處理者或未後處理者)可藉由依標的摻雜而上標籤，利用具有變化含量的同位素(13C、18O、15N及/或34S)的難溶而對熱穩定的無機物質摻雜。舉例而言，對於這種摻雜作用，舉例而言，而用難溶含氧的無機Al、Ba、Si、Ti、Zr、Ca、Mg、Fe、Zn及/或B的化合物。這些無機化合物並不一定要為氧化物性質者，而可含有例如陰離子，如氫氧化物、磷酸塩、碳酸塩、硝酸塩、硫化物或硫酸塩。
同樣地可將上述方法作任意組合，利用這些方法，可使該無機填充物及/或色素長期用重同位素上標籤。
利用上述方法上標籤的無機填充物及/或色素也可用於填充物及/或色素的所有應用領域，例如當作色素及/或填充料，例如在：a)塑膠/聚合物材料(例如寶特瓶、膜/箔片、合成及化學纖維)；b)顏料與漆；c)食品；d)醫藥品；e)化粧品；f)紙；h)玻璃；i)飼料；本發明的標的之細節為：--一種無機填充物及/或色素，它利用重而穩定的同位素上標籤；--一種無機填充物及/或色素，它利用重而穩定的同位素上標籤，其中該標籤牢固地建構在該填充物及/或色素中；--一種無機填充物及/或色素，它長期地利用重而穩定的同位素上標籤；--一種無機填充物及/或色素，其用於作標籤的同位素的含量不會受熱處理影響；--一種無機填充物及/或色素，它利用重而穩定的同位素上標籤，其中該同位素由以下物的一種或數種選 出：2H、13C、15N、18O及34S；--一種無機填充物及/或色素，它用重而穩定的同位素上標籤，其中該同位素係較自然多者；--一種無機填充物及/或色素，它用重而穩定的同位素上標籤，其中該同位素係較自然少者；--一種無機填充物及/或色素，它利用重而穩定的同位素上標籤，其中該填充物及/或色素本身上標籤；--一種無機填充物及/或色素，它利用重而穩定的同位素上標籤，其中將該填充物及/或色素粒子外的鍍層上標籤；--一種無機填充物及/或色素，它利用重而穩定的同位素上標籤，其中該同位素係含在填充物及/或色素之依標的之摻雜物中；--一種無機填充物及/或色素，它利用重而穩定的同位素上標籤，其中△δ值在3~1000‰之間，且宜在5~300‰之間，尤宜在10~200‰之間，及/或在-3~100‰之間，尤宜在-5~-20‰之間；--一種無機填充物及/或色素，它利用重而穩定的同位素加標籤，其中該填充物及/或色素為一種色素及/或填充料；--一種無機填充物及/或色素，它利用重而穩定的同位素加標籤，其中該填充物及/或色素為TiO2、ZnS或BaSO4；--一種製造加標籤的無機填充物及/或色素的方 法；--一種製造加標籤的無機填充物及/或色素的方法，其中該標籤牢固地建入在填充物及/或色素中；--一種製造加標籤的無機填充物及/或色素的方法，其中該標籤由一種或數種重而穩定的同位素及/或其化合物造成；--一種製造加標籤的無機填充物及/或色素的方法，其中該同位素由以下物之一種或數種選出：2H、13C、15N、18O及/或34S；--一種製造加標籤的無機填充物及/或色素的方法，其中該同位素的量比自然者多；--一種製造加標籤的無機填充物及/或色素的方法，其中該同位素的量比自然者少；--一種製造加標籤的無機填充物及/或色素的方法，其中該填充物及/或色素在製造時，將一種重而穩定的同位素建入該填充物及/或色素的化合物中而上標籤；--一種製造標籤的無機填充物及/或色素的方法，其中該填充物及/或色素在作無機式及/或有機式後處理時用重而穩定的同位素上標籤；--一種製造加標籤的無機填充物及/或色素的方法，其中該填充物及/或色素利用難溶之熱穩定的無機物質標的作摻雜而上標籤；--一種製造加標籤的無機填充物及/或色素的方法，其中該填充物及/或色素係為色素及/或填充料； --一種製造加標籤的無機填充物及/或色素的方法，其中該填充物及/或色素為TiO2、ZnS或BaSO4；--一種製造加標籤的無機填充物及/或色素的方法，其中TiO2或BaSO4中的18O含量提高；--一種製造加標籤之無機填充物及/或色素的方法，其中ZnS或BaSO4中的34S含量提高；--一種製造加標籤的無機填充物及/或色素的方法，其中在TiO2、ZnS或BaSO4的無機式及/或有機或後處理中，18O含量利用鋁、矽、鋯、錳及/或鈦的用18O上標籤的氧化物或氫氧化物而將18O含量提高。
--一種製造加標籤的無機填充物及/或色素的方法，其中在有機式後處理中，2H、13C、15N、18O及/或34S的含量利用含不同含量之同位素2H、13C、18O、15N及/或34S的多元醇、胺化合物及/或矽力康油作表面處理而提高或降低；--使用本發明的填充物及/或色素當作填充料及/或色素；--在製造塑膠/聚合物材料(寶特瓶、膜/箔片、合成及化學纖維)、色素與漆、食品、醫藥劑、化粧品、橡膠、玻璃、飼料時加其加工時，使用本發明的填充物及/或色素，特別是當作色素及/或填充料用。
本發明茲利用以下實施詳細說明。但其範圍不限於此。
〔實例1：製造加標籤的無機填充物及/或色素〕
(a)提高TiO2或BaSO4中的18O含量；
i)將含鈦化合物如四氯化鐵用加了18O標籤的水水解製造TiO2，該反應造成一種TiO2產物，其δ(18O)為+50‰；而未加標籤的TiO2產物的δ(18O)值則為-2.7‰；因此△δ值為+52.7‰；ii)將含鈦化合物如硫酸鈦氧溶液用含18O的水作水解製造TiO2；iii)藉著用標有18O標籤的硫酸由氯化鋇水溶液製造BaSO4並沈澱，此反應造成一種BaSO4產物，δ(18O)值為+33‰；而未加標籤的BaSO4產物的δ(18O)值為-3‰；因此△δ值為+36‰。
(b)提高ZnS或BaSO4中的34S含量
i)將ZnO與帶有34S標籤的硫酸反應成硫酸鋅，然後與Na2S反應成ZnS而製造ZnS；ii)利用加34S標籤的硫酸由氯化鋇水溶液製造BaSO4並沈澱出來。
〔實例2：製造無機填充物及/或色素(其鍍層中加標籤)〕
(a)在TiO2、ZnS或BaSO4的無機及/或有機後處理中將18O含量提高。在無機後處理時，係將難溶無色無機化合物沈積到個別的色素粒子上。舉例而言，要作表面處理，係使用鋁、矽、鋯、錳及/或鈦的氧化物或氫氧化物。此沈積反應可使用加以18O標籤的原料而進行。
(b)在TiO2、ZnS或BaSO4的有機後處理中將2H、13C、15N及/或18O的含量提高，舉例而言，要將填充料與色素作後處理，係使用化合物如多元醇、胺化合物或矽力康油。這些化合物也隨添加入進入終產物，且因此可當作標籤檢出。
〔實例3：利用依標的之摻雜製造加標籤的色素或填充料〕
(a)將TiO2用加了18O標籤的ZrO2摻雜；(b)將ZnS用加了13C標籤的CaCO3摻雜；(c)將BaSO4用加了15N及/或18O標籤的MgNH4PO4摻雜；(d)將TiO2用加了18O標籤的BaSO4摻雜，將用1重量%之用18O上標籤的BaSO4摻雜；將用1重量%之用18O上標籤的BaSO4加到TiO2色素，在摻雜的終產物中造成δ(18O)值為+162‰；將用1重量%之未加標籤的BaSO4加到TiO2色素則在摻雜的產物中造成δ(18O)值為-3‰。因此△δ值為+165‰。
實例1~3同樣可作任意組合。

Claims (12)

  1. 一種無機填充物及/或色素，由以下之物選出：TiO2、ZnS或BaSO4，該無機填充物及/或色素利用重而穩定的同位素加標籤，其特徵在：該標籤物牢牢地建入在該無機填充物及/或色素，其中該填充物及/或色素相較於天然產出的同成分化合物來，具有較高之正△δ值或較低的負△δ值，且當作標籤物用的同位素含量不會受熱處理影響，其中在一預定的無機填充物及/或色素的場合△δ有一恆定值，在此值時同位素含量升高或減少，且△δ值在100‰及1000‰之間。
  2. 如申請專利範圍第1項之無機填充物及/或色素，其中：該同位素由18O及/或34S選出。
  3. 如申請專利範圍第1或第2項之無機填充物及/或色素，其中：該填充物及/或色素本身加標籤。
  4. 如申請專利範圍第1或第2項之無機填充物及/或色素，其中：填充物及/或色素的鍍層中加標籤。
  5. 如申請專利範圍第1或第2項之無機填充物及/或色素，其中：該△δ值在3~1000‰間，且宜在5~300‰間，尤宜在10~200‰間，及/或-3~-100‰之間，尤宜在-5及 -20‰之間。
  6. 一種用於製造申請專利範圍第1至第5項中任一項的無機填充物及/或色素的方法，其中：該標籤物牢牢建入到填充物及/或色素的化合物中。
  7. 如申請專利範圍第6項之方法，其中：在製造時，藉著將適合的重而穩定的同位素建入該化合物中而作長久性的加標籤。
  8. 如申請專利範圍第6項之方法，其中：該無機填充物及/或色素在作無機式及/或有機式後處理時用重而穩定的同位素作長久性的加標籤。
  9. 如申請專利範圍第6或第7項之方法，其中：將TiO2或BaSO4中的18O含量提高。
  10. 如申請專利範圍第6或第7項之方法，其中：將該ZnS或BaSO4中的34S含量提高。
  11. 如申請專利範圍第6或第7項之方法，其中：在TiO2、ZnS或BaSO4的無機式及/或有機式後處理中，利用鋁、矽、鋯、錳及/或鈦的用18O加標籤的氧化物或氫氧化物而將18O含量提高。
  12. 一種如申請專利範圍第1到第5項中任一項之無機填充物及/或色素的應用，其中：其係用於將塑膠/聚合物材料、顏料、油漆、食品、醫藥、化粧品、紙、橡膠、玻璃、飼料，特別是用於作色素及/或填充料。
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002329179A (ja) * 2001-04-27 2002-11-15 Tokyo Gas Co Ltd ダイヤモンドを用いた識別マーク

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0206820A3 (en) * 1985-06-27 1987-10-28 De Beers Industrial Diamond Division (Proprietary) Limited Diamond synthesis
AU634601B2 (en) * 1989-12-11 1993-02-25 General Electric Company Single-crystal diamond of very high thermal conductivity
CA2030049A1 (en) * 1989-12-11 1991-06-12 Thomas R. Anthony Single-crystal diamond of very high thermal conductivity
US5038046A (en) * 1990-07-10 1991-08-06 Biotechnetics Method and generator for producing radioactive lead-212
US5286468A (en) * 1991-02-21 1994-02-15 Ontario Hydro Producing carbon-14 isotope from spent resin waste
ZA927268B (en) * 1991-10-14 1993-03-25 De Beers Ind Diamond Ultra-hard abrasive particles.
US5391354A (en) * 1993-08-30 1995-02-21 General Electric Company Process for gas phase conversion of diethylzinc to zinc oxide powder
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FR2777478B1 (fr) * 1998-04-17 2000-06-16 Roquette Freres Dispersion aqueuse de pigment(s) et/ou charge(s) contenant une composition saccharidique particuliere
US20030039865A1 (en) * 2001-06-20 2003-02-27 Isonics Corporation Isotopically engineered optical materials
CN1129636C (zh) * 2001-07-09 2003-12-03 师永昌 纳米材料改性橡胶弹性体制作塑胶跑道场地的方法
JP2003025775A (ja) * 2001-07-10 2003-01-29 Tokyo Gas Co Ltd 識別マーク
JP4964372B2 (ja) * 2001-07-17 2012-06-27 独立行政法人産業技術総合研究所 炭素材料の製造方法
CA2454890A1 (en) * 2001-08-08 2003-02-20 Theragenics Corporation Use of isotopes to provide information to an article
DE10200802A1 (de) * 2002-01-11 2003-07-31 Forschungszentrum Juelich Gmbh Verfahren zur Identifizierung von Stoffen, die mit deuteriertem Wasser markiert sind
NZ547675A (en) * 2003-12-05 2010-06-25 Duluxgroup Australia Pty Ltd Tagged polymeric materials and methods for their preparation
US20060236470A1 (en) * 2005-03-29 2006-10-26 Sabnis Ram W Novelty compositions with color changing indicator
US20070111314A1 (en) * 2005-11-08 2007-05-17 Lufei Lin Methods for tagging and authenticating inks using compositions
JP5307195B2 (ja) * 2011-06-16 2013-10-02 独立行政法人産業技術総合研究所 同位体比率を制御した炭素材料及び識別マーク

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002329179A (ja) * 2001-04-27 2002-11-15 Tokyo Gas Co Ltd ダイヤモンドを用いた識別マーク

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